FI93721B - Dieters useful in the preparation of Ziegler-Natta catalysts - Google Patents

Description

93721

Dieters useful in the preparation of Ziegler-Natta catalysts

The present invention relates to novel dieters.

The diethers of the invention are useful as fuel additives (thereby increasing octane number), as solvents, as metal ion complexing agents, and in the preparation of Ziegler-Natta catalysts.

10 Dieters have the general formula:

rII rIII

r1 '^ c —- 0RVI1 (I)

15 -RT -0RVI

RIV XRV

wherein R and R1 are the same or different and each represent a branched C3-18 alkyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, phenyl or benzyl or R and R1 together with the carbon atom to which they are attached form a cyclohexyl or norbornyl, R11, R111, RIV and Rv are hydrogen and RVI and RVI1 are the same or different and represent C1-6 alkyl.

The new diethers can be prepared by various methods. For example, they can be prepared by known etherification reactions, for example those listed below, starting from the corresponding diol having the structure:

R11 R11

R1 ^ C —-OH

(II)

35 R · ^ -OH

RIV ^ Rv 2 93721 1) Reaction of diols of formula II or corresponding basic alcoholates with compounds of formulas RVI-X and RV1I-X or mixtures thereof (wherein X = Cl, Br, I, C6H5-SO3, p-CH3C6H5SO3, CH3SO3) wherein R, R1, R11, R111, RIV and Rv are as defined above.

2) Reaction of diols of formula II with dialkyl sulfates of formulas R2VIS04 or R2V1IS04 in a basic medium.

3) RII Rlll of derivatives of general formula III derived from diols of formula II

R X

(II)

15 R1 -X

RIV ^ R * (where R - Rv and X are as defined above) with alcoholates of the reaction formulas RVI-0M and RVI1-0M, wherein M = Na, K, Mg, Ca or a mixture thereof.

4) Thermal or catalytic dehydration of mixtures of diols of the general formula II with alcohols of the formula RVI0H or RVII0H or mixtures thereof.

These and other suitable methods are described in 1) Houben Weil - Methoden der Organischen Chemie Vol VI / 3 Verlag ed. Stuttgard 1965.

2) G.W. Gokel and Coll. Synthesis 1976, 168 3) G. Johns and Coll. ibid. 1976, 515 30 4) D. Achet and Coll, ibid 1986, 642.

Diols of general formula (II) can in turn be prepared by known methods, for example by reduction from the corresponding diesters, dialdehydes, diketones, ketoaldehyde or dicarboxylic acids of general formula IV and V, as well as from ketoesters of general formula (VI) and aldehydes. - 3 93721 of grains: / R11 R11

/ I

R COOR R 1 .C = O R C = O

R1 ^ COOR R1 = O R1 '^ COOR

V11 (IV) (V) (VI) 10 (wherein the radicals R, R1, R11, R111 have the same meaning as above).

Examples of these methods are given in: H. Adkins, Organic Reactions 8, 1 (1954) 15 - N.G. Gaylord, Reduction with Complewx Metal Hydrides,

Interscience Publishers, N.Y., London 1956 - R.F. Nyström, W.G. Brown, J. Am. Chem. Soc. 69, 1197 (1947).

Diols of formula II (wherein R 11, R 111, RIV and 20 Rv are H) can also be further prepared according to general formula VII from aldehydes R 1 -CH-CHO (VII) 25 R 1 wherein R and R 'are as defined above, the basic formaldehyde according to the Cannizzaro reaction (see, e.g., Organic Reactions Vol. II, p. 30 94 - J. While ed. - NY, 1944).

The diols of the general formula II can be easily converted into the corresponding III derivatives by known methods (see Houben Weil, Methoden der organischen Chemie, Band V / 3, V / 4, IX; Verlag ed. Stuttgard).

The following examples illustrate the following ethers according to the invention 4 93721 and processes for their preparation: 2-methyl-2-isopropyl-1,3-dimethoxypropane-2,2-diisobutyl-1,3-dimethoxypropane-2,2-diphenyl-1 1,3-dimethoxypropane 5-2,2-dibenzyl-1,3-dimethoxypropane-2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane-2,2-diisobutyl-1,3-dibutoxypropane-2,2 -diisobutyl-1,3-diethoxypropane-2-isopentyl-2-isopropyl-1,3-dimethoxypropane 10-1,1-bismethoxymethylcyclohexane - (+/-) 2,2-bis (methoxymethyl) norbornane (racemic mixture) ,

Other examples of ethers are: 2-isopropyl-2- (3,7-dimethyloctyl) -1,3-dimethoxy-15-cipropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-isopropyl-2- cyclohexylmethyl-1,3-dimethoxypropane, 2,2-diisopentyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1, 3-dimethoxypropane, 2,2-dicyclopen-20-style-1,3-dimethoxypropane, 2-heptyl-2-pentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-ipropyl 2-iobutyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane.

Example 1 Preparation of 2,2-diisobutyl-1,3-dimethoxypropane a) Preparation of diisobutylethyl malonate A 250 ml flask equipped with a stirrer, condenser, dropping funnel, thermometer and gas flow tube was charged with 100 g of anhydrous ethanol and 5 g of nitrogen under a stream of nitrogen. (0.22 mol) Na.

When the Na was completely dissolved, 16 g (0.1 mol) of diethyl malonate was added and stirred at room temperature for a few minutes. 28 g of isobutyl bromide (0.21 mol) were then added and the mixture was refluxed with 35 l of 5,93721 with stirring for 6 hours. Then 7.5 g of dry sodium ethylate (0.12 mol) and 4 g of isobutyl bromide (0.1 mol) were added. Stirring and refluxing were continued for another 8 hours.

Most of the solvent was distilled off under reduced pressure (50 minHg) and the residue was extracted with 200 ml of hexane. From the distilled hexane solution, 15.5 g of diisobutylethyl malonate with a boiling point of 145-146 ° C / 20 mmHg were obtained. The gas chromatographic purity of the product 10 (main peak area) was 97.5%, which is consistent with Bently and Perkin J. Chem. Soc. 73, 61 with a sample of diisobutylethyl malonate.

b) Preparation of 2,2-diisobutyl-1,3-propanediol

100 ml of diethyl ether and 3 g of LiAlH 4 (0.079 mol) were introduced into the same apparatus as in a) above under a stream of nitrogen.

15.5 g of diisobutylethyl malonate prepared in a) above were then added dropwise over 1 hour with vigorous stirring and the mixture was refluxed for 20 minutes.

The reaction mixture was then dropped into a vessel containing 100 g of ice acidified with dilute HCl and extracted with three 100 mL portions of ethyl ether.

The ether was evaporated to give 10 g of crude α-25, which crystallized from hexane to give 8.5 g of 2,2-diisobutyl-1,3-propanediol, m.p. 75-77 ° C and Elemental analysis C = 70.3 % and H = 12.6%. The theoretical value for CuH2402 is C = 70.21% and H = 12.7%.

c) Preparation of 2,2-diisobutyl-1,3-dimethoxypropane

To the same apparatus as in (a) above, 8.5 g (0.06 mol) of 2,2-diisobutyl-1,3-propanediol, 200 ml of dioxane and 15.4 g (0.136 mol) of potassium tert-one were added under nitrogen. butylate.

The mixture was stirred at room temperature for 30 minutes and then 20 g of CH 3 I (0.14 mol) were added. During the addition, the temperature automatically rises to 50 ° C.

After 9 h, additional potassium tert-butylate (154 g, 0.136 mol) and CH 3 I (20 g, 0.14 mol) were added and the mixture was refluxed for 1 h.

The reaction mass was filtered and the filtrate was distilled under reduced pressure. Among other products, 7.4 g of 2,2-diisobutyl-1,3-dimethoxypropane having a boiling point of 100-101 ° C / 22 mmHg and a purity by gas chromatography (GLC) of 99% (area of the chromatography peak) were obtained. ).

10 n ° 0 = 1.4337.

1 HNMR (300 MHz, CDCl 3, TMS internal standard): peaks 0.89 ppm, doublet 12 H

1.21 ppm, doublet 4 H

1.68 ppm, multiplet 2 H 3.16 ppm, singlet 4 H

3.26 ppm, singlet 6 H

Using the above methods a), b) and c), the following compounds were obtained: 1) 2-methyl-2-isopropyl-1,3-dimethoxypropane 20 n 2 O = 1.4209, boiling point 160-161 ° C / 760 mmHg 2) 2, 2-dibenzyl-1,3-dimethoxypropane freezing point 105 ° C (from petroleum ether) 3) 2,2-diisobutyl-1,3-dibutoxypropane n 2 O = 1.4378, boiling point 115-117 ° C / 1 mmHg 25 4) 2 , 2-diisobutyl-1,3-diethoxypropane n 2 O = 1.4302, boiling point 118-120 ° C / 20 mmHg

Example 2 Preparation of 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane A stainless steel autoclave with an anchor stirring system was charged with 5.8 g (0.02 mol) of (C6H5CH2) 2C (CH2OCH3) prepared according to Example 1. ) 2, 100 ml of n-hexane and 10 g of Raney Ni, which had been washed by decanting with 3 parts of 50 cm3 of anhydrous ethanol and then with 35 parts of 50 cm3 of hexane.

ii 7 93721

The autoclave was pressurized with hydrogen to 17 atm and heated to 135 ° C (internal temperature) for 8 hours with stirring.

After cooling, the catalyst was filtered off from the reaction mixture and evaporated in vacuo to give 5.9 g of a colorless oil with a purity of 99% n 2 O = 1.4790. The only compound detected by thin layer chromatography (TLC) was 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane. 1 HNMR (300 MHz, CDCl 3, TMS as internal standard):

10 Peak: 0.96 ppm multiplet 4 H

1.18 ppm multiplet 12 H

1.63 ppm multiplet 10 H 3.15 ppm singlet 4 H

3.27 ppm singlet 6 H 15 Example 3 Preparation of 2,2-diphenyl-1,3-dimethoxypropane a) Preparation of 2,2-diphenyl-1,3-propanediol

To the same apparatus as in Example 1 (a) above was added 10.6 g (0.054 mol) of (C 6 H 5) 2 CHCHO (Fluca), 4.03 g (0.028 mol) of K 2 CO 3, 10 cm 3 of water, 13.2 ml of 40% formaldehyde. aqueous solution (0.176 mol) and 35 ml of 99% pure ethanol.

The mixture was stirred and refluxed for 6 hours, cooled and diluted with 200 ml of water. The precipitate thus formed was filtered, washed with water and crystallized from benzene to give 9.6 g of 2,2-diphenyl-1,3-propanediol, m.p. 102-104 ° C.

b) Preparation of 2,2-diphenyl-1,3-dimethoxypropane 30.6 g of 2,2-diphenyl-1,3-propanediol dissolved in 400 ml of anhydrous tetrahydrofuran were placed in the same apparatus as in a) above and stirred under nitrogen. washed with 3.8 g NaH (55% NaH dispersed in petrolatum) until hydrogen evolution ceased. Over 20 minutes, 9.6 mL of CH 3 I was added and stirred continuously for 2 hours. Most of the THF distilled off; the product was then diluted with 8,93721 water (200 mL) and extracted with two 50 mL portions of diethyl ether. The ether extract yielded, by vacuum distillation, 3.5 g of 2,2-diphenyl-1,3-dimethoxypropane, b.p. 188-190 ° C / 20 mmHg, which was consistent with TLC chromatography and had n = 1 , 5558.

By the same procedure as in a) and b) above, the following compounds were prepared starting from hexahydrobenzene aldehyde and norbornane-2-carboxaldehyde, respectively.

10 A) 1,1-Bismethoxymethylcyclohexane

boiling point 97-98 ° C / 20 mmHg; η30 = 1.4487 XHNMR (300 MHz, CDCl 3, TMS as internal standard): peaks: 1.36 ppm multiplet 10 H

3.20 ppm singlet 4 H

3.29 ppm singlet 6 H

B) (+/-) - 2,2-bismethoxymethylnorbornane boiling point 106-108 ° C / 20 mmHg; n30 = 1.4659: HNMR (300 MHz, CDCl3, TMS as internal standard):

Peaks: 0.72 ppm doublet 1H H 1.14 ppm doublet 1H

1.06 ppm multiplet 1H

1.34 multiplet 2 H

1.51 ppm multiplet 3 H

1.97 ppm singlet (broad) 1H 25 2.15 ppm singlet (broad) 1H

3.06 ppm AB system 1H 3.14 ppm AB system 1H 3.33 ppm AB system 1H

3.36 ppm AB system 1H

30 3.29 ppm multiplet 6 H

Example 4 (non-compliant) Preparation of 2,2,4-trimethyl-1,3-dimethoxypentane A 2 L flask equipped with a stirrer, condenser, dropping funnel, thermometer and gas flow tube was placed under 35 nitrogen streams: (· 9 93721 29, 2 g (0.2 mol) of 2,2,4-trimethyl-1,3-propanediol, 600 ml of dioxane and 10 g (0.2 mol) of NaH at a concentration of 50% in petrolatum oil were stirred until gas evolution occurred. ceased, then heated to 80 ° C and 18 mL of CH 3 I (0.28 mol) was added dropwise.

After 2 h, 10 g of NaH at a concentration of 50% in petrolatum oil and 40 cm3 of CH3I were added.

After refluxing for 8 hours, the reaction mixture was diluted with 1.5 L of water and extracted with 3 portions of hexane-10 (100 mL each).

The extract was washed with water and dried, and vacuum distillation gave 22.5 g of 2,2,4-trimethyl-1,3-dimethoxypropane having a boiling point of 105 ° C / 70 mmHg and a GLC purity (peak area ) was 98.6% and had 15 n ° 0 = 1.4227 1 HNMR (60 MHz, CDCl 3, TMS as internal standard):

Peaks: 1.5 ppm multiplet 12 H

3.7 ppm multiplet 3 H

4.1 ppm multiplet 6 H

Example 5 Preparation of 2-i-sopentyl-2-isopropyl-1,3-dimethoxypropane a) Preparation of isopentylidene-isopentanal 50 g of isopentanal are reacted according to DRP-643 341 (1933 IGFarb.) And DRP-544 192 (1933 I.

G. Farb.).

27 g of 2-isopentylidene-isopentanal with a boiling point of 98-102 ° C / 20 mmHg were obtained.

b) Preparation of 2-isopentylisopentanal 30 J.V. Braun and G. Manz, Ber. 1969, 67 (1934) starting from 27 g of 2-isopentylidene-isopentanal gave 27 g of crude material which was not studied. The measured hydrogen absorption was in accordance with the reaction shown.

10 93721 c) Preparation of 2-isopropyl-2-isopentyl-1,3-propanediol

In the same apparatus as in Example 1 (a) above, 27 g of the crude 5 aldehyde prepared in b) above, 16 g of K 2 CO 3, 200 ml of 99% pure ethanol and 52 ml of anhydrous 40% CH 2 O were introduced and allowed to reflux with stirring for 4 hours. The reaction mixture was then diluted with 1 L of water, extracted with two 250 mL portions of ether. The ether was evaporated and the ether extract was dried and distilled under reduced pressure to give (among other compounds) 9 g of 2-isopropyl-2-isopentyl-1,3-propanediol, boiling point 165 ° C / 20 mmHg and uniform in TLC analysis. with. The material was used in the next reaction without further analysis.

15 d) Preparation of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane

9 g of the raw material from c) above, 200 cm3 of dioxane and 15 g of (CH3) 3COK (potassium tert-butylate) were placed in the apparatus of Example 1 a) under a stream of nitrogen and stirred for about 30 minutes. 10 mL of CH 3 I was then added over 1 hour and the materials were refluxed for 5 hours. The reaction mixture was diluted with 1 L of water and extracted with diethyl ether. The ether was evaporated and the ether extract was dried and distilled under reduced pressure. Among other products, 7.3 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane having a boiling point of 130-133 ° C: / 35 mmHg and a gas chromatographic purity of 98.6% (peak areas) were obtained. n ° 0 = 1.4365: HNMR (300 MHz, CDCl 3, TMS as internal standard) silicon-30 kit:

0.87 ppm doublet 6 H

8.89 ppm doublet 6 H

1.11 ppm multiplet 2 H

1.28 ppm multiplet 2 H

ti U 93721

1.42 ppm multiplet 1H

1.76 ppm multiplet 1H

3.23 ppm singlet 2 H

3.24 ppm singlet 2 H

Example 6 60 ml of n-heptane and 67 ml of tetra-n-butoxytitanium were introduced into a 500 ml flask with stirring and heated to 45 ° C. Over a three hour period, a solution of AlEt 2 Cl (44.8 mL) in n-heptane 10 (108 mL) was gradually added. The temperature was raised to 60 ° C for one hour and then cooled to room temperature. The solid was separated and washed four times with 100 ml portions of heptane and then dried in vacuo.

8.1 g of this solid were introduced into the flask together with 20.3 mmol of titanium tetrachloride, 20.3 ml of toluene and 20.3 mmol of 2,2-diisobutyl-1,3-dimethoxypropane and heated to 60 ° C per hour and then to 100 ° C. At C for 4 hours. The reaction mixture was then cooled to room temperature, the solid product was separated, washed with 20 n-heptane until no chlorine ions remained in the filtrate and dried in an oven under a stream of nitrogen.

After a stream of nitrogen-dried, 120 mg of an AlEt 2 Cl, 12.4 mg of the solid prepared above and 80 ml of liquid propylene were introduced into a 120 ml autoclave equipped with a magnetic stirrer and heated to 60 ° C and kept at this temperature for 1 hour with stirring. Excess unreacted propylene was removed to give 16.9 g of polypropylene with an isotacticity index of 96.8% (by boiling n-heptane extraction for 4 hours).

Claims (2)

12 93721 Diether, characterized in that it has the formula I 5 ri Rm R1. C —- ORVI1 (I) R ^^ ^ "\ C-- 0RVI / \ Rlv Rv wherein R and R1 are the same or different and each represent branched C3-18 alkyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, phenyl or benzyl, or R and R1 together with the carbon atom to which they are attached form cyclohexyl. or a norbornyl group, R ", R111, RIV and Rv are hydrogen and RVI and RVI1 are the same or different and represent C1-6 alkyl. Diether according to Claim 1, characterized in that it is 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, -isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1, 3-dimethoxypropane or 2,2-dicyclohexyl-1,3-dimethoxypropane. 13 93721